Production of new azo dyestuffs on cellulose materials



I Patented Nov. 11, 1941 I the colouring of cellulosicmaterial by causing the the fibreilwith diazotised aromatic amines.

- It is an objector invention to producead- -vantageous results in. the colouring and printing of cellulosictextilematerial, A further object is to provide j'newj chemical compounds which are said 2:3-hydroxynaphthoic amides to couple on useful in the art of colouring cellulosic textilematerial. Another object is to provide a method for preparing. such new chemical compounds. Still another objectis'to provide'new compositions of matter'jandto'jadvance the art. Other objects will" appear hereinafter.

According to 'th'e'invention amines which are 4 amino -2z5=di(p=aeetoxyethoxy) -anilides of benzoiq acid and phenoxyacetic acids, which acids may carry as nuclear substituents, for example, alkoxy or halogen, are condensed with 2:3-hydroxynaphthoic===acid,or a reactive derivative thereof, andyhydrolysed so as to produce the new corresponding 2:3-hydr0xynaphthoic-2:5- di(B-hydroxyethoxy)"-tanilides which are reactive towards diazo compounds.

:Thus there: mayiabe-"employed, in accordance with-the, invention, 4 'ethcxy) anilides Zof; for; example, the-following acids, benzoicyacidyzlo-chlorobennoic acid, mbromobenzoic acid, p-methoxybenzoic acid, and phenoxyacetic acid. *i 12 By a further feature oi the invention the said 2'; 3-hydroxynaphthoic anilides are .applied to cellulosic .fibre an the material coloured by the application thereto ar a" diaz'ocompound, which is, free of solubilising groups such as sulphonic acid or carboxylicacid-g'lpups; jfThe diazo como n ma b a e ai a i is m. s in the i'ornr'cf a metallic double s'alt or an arylsul- Ph c wit 'f o l't. e h ni l the purpo e-or diazo components there maybeemploy onex'amplaithe followamines: c-chlojroanilinc,

: n qsrATEs PATE J fgrn'onocrron or NEW AZO DYESTUFFS 0N I CELLULOSE MATERIALS -G'eofl'rey"Jones. Marriott and Kenneth Herbert Saunders, .Blackley, Manchester, England, as-

,signors to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application December 21, 1939, Serial No. 310,440. In Great Britain January 18 Claims. (obs-4c) .shades are obtained of surprisingly good light OFICE fastness. Also the 2:3-hydroxynaphthoic-2':5'- di(fl-hydroxyethoxy) -anilides described above,

which are used as coupling components, possess only small to medium aflinity for the fibre. This is an advantage when they are used by textile printers since the uncoloured portions of the printed fabric can be easily .washed' to give a clear white. Moreover the shades obtained are capable of being dischargedto a good clear white.

The 4-9. m in o 2:5'- di (p-acetoxyethoxy) anilides referred to above, can be made by inter-' acting 2:5-di(p-acetoxyethoxy) aniline with the requisite carboxylic acid halide, and then nitrating and reducing. 2':5-di(p-aceto:wetho'xy) aniline can be made as described in British specification No. 422,417.'

The invention is illustrated but not limited by the following examples,in which the parts are by weight.

under reflux for 15 hours, poured into water and the aqueous layer made alkaline with sodium carbonate and the toluene removed by steam distillation. The insoluble material is filtered ofl, washed and dissolved in'a boiling solution of 10 parts of sodium hydroxide in 600 parts of water.

The solution so obtained is cooled,filtered and the new amide, of constitution 2:3-hydroxynaphthoic 2' :5 di(p -hydroxyethoxy)--4'-ben zoylamino anilid'e, precipitated'by the addition of acid, filtered off and dried. 1

4-benzoylamino-2 5-'di(p-acetoxyethoxy) aniline (M. P. 110C.) may'be niadeby condensin benzoyl chloride with. I 2 i 5.-di (,B-acetoxyethoxy) aniline in benzene in the presence; ofpota sslum acetate followed by nitration in glacial acetic acid and reduction of the resulting benzoyl compound.

Example 2 5-parts of the new amide made according to Example 1 are made into a paste with' lo-partsgof hydroxide solution (S. I}G."; 1.31). The resulting solution i diluted with775parts or cold water an We? for 20 minutes, removed, squeezed well and then introduced into a bath containing 2 parts of diazotised p-chloro o-nitroaniline per 1000 parts of solution. The cotton is turned for 20 min utes in the bath, removed, squeezed, rinsed well Amine employed Shade obtained m-Chloroaniline Brownish red. 2:5Pdlchloroaniline Orange brown. m-aminoanthraquinone Brown. dchloro-Z-aminotoluena. Dull red. 51nltro-2-aminoanisole Dull maroon. 4-nitro-2-aminoanisole Dull red.

- Example 3 20 parts of *i-(phenoxyacetylamino) -2:5-di(pacetoxyethoxy) aniline, which may be made as described below, are heated to 80 C., with stirring in 300 parts of toluene together with 10 parts of 2:3-hydroxynaphthoic acid whilst 2.5 parts of phosphorus trichloride are added dropwise during 20 minutes. The mixture is then boiled under reflux for 16 hours and the toluene removed and the new amide of constitution 2:3- hydroxynaphthoic-2' di (5 hydroxyethoxy) d'-phenoxyacetylamino anilide prepared as described in Example 1.

4- (phenoxyacetylamino) -2 5-di(p-acetoxyethon) -aniline (M. P.109 C.) may be made by condensing phenoxyacetyl chloride with 2 5-di(fiacetoxyethoxy) -aniline in benzene in the presence of sodium acetate followed by nitration in glacial acetic acid and reduction of the resulting phenoxy-acetyl compound. 1

Example 4 3 parts of the new amide made according to Example 3 are made into apaste with parts of 50% Turkey red oil, which has been neutrahsed with sodium carbonate, and 60 parts of boiling water are added followed by 6 parts of sodium hydroxide solution (S. G. 1.31).- Boiling is continued until a clear solution is obtained which is then diluted with 920 parts of cold water. 50

parts of cotton yarn are immersed in this solu- Amine employed Shade obtained o-Nitroaniline Oran e 2:5-dlchloroaniline iamw'im ifi i' waminuanthraqumone... Orange brown. dclgloromotoluene Red. 5-n tro-2-aminoanisole Dull red. 4-mtrc-2-aminoanisole Red. I

Example 5 j 22.3 parts oi 4'-p-anisoylamino-2:5-di(pacetoxyethoxy) aniline, which may be made as described below, are heated with stirring in 300 parts of toluene at 60 C. together with 9.5 parts of 2:3hydroxynaphthoic acid, and 2.7 parts of phosphorus trichloride are added drop by drop during one hour.- The mixture is then boiled under reflux for 15 hours, poured into water and the aqueous layer made alkaline with sodium carbonate and the toluene removed by steam distillation. The insoluble material is filtered ofl, washed and dissolved in a boiling solution of 10 parts of sodium hydroxide in 600 parts of water. The solution so'obtained is cooled, filtered and the new amide of constitution 2:3- hydroxynaphthoic-2' :5- di ()8 hydroxyethoxy) 4'-p-anisoylamino anilide, M. P. 230 C., precipi-.

tated by the addition of acid, filtered ofi and dried.

i-p-anisoylamino-2 5-di(p-acetoxyethoxy) aniline (M. P. 127-128 C.) may be made by condensing p-anisoyl chloride with 2:5-di(B-acetoxyethoxy) aniline in benzene in the presence of potassium acetate, followed by nitration in glacial acetic acid and reduction of the resulting p-anisoyl compound.

Example 6 White cotton cloth ispadded in a solution of 15 parts of the new amide made according to Example 5, 25 parts of 50% Turkey red oil, which has been neutralised with sodium carbonate, and 20 parts of sodium hydroxide solution (S. G. 1.31) in 940 parts of water. The cloth is then printed with a printing paste containing:

Parts Zinc chloride double salt of anthraquinone- I-diazonium rhlm-idn 2 12% mucilage of wheat starch-traga- I canth (6:1) 40% acetic acid 2 Water 36 Example 7 24.7 parts of 4-m-bromobenzoylamino-2z5- di(p-acetoxyethoxy) aniline, which may be made as described below, are heated with stirring in 300 parts of toluene at 60 C. together with 9.5 parts of 2:3-hydroxynaphthoic' acid, and 2.7 parts of phosphorus trichloride are added drop by drop during one hour. The mixture is then boiled under reflux for 15 hours, poured into water and the aqueous layer made alkaline with sodium carbonate and the toluene removed by steam distillation. The insoluble-material is filtered oil, washed and dissolved'in a boiling solution of 10 parts of sodium hydroxide in 1000 parts or water. The solution so obtained is cooled, filtered and the new amide of constitution 2:3- hydroxynaphthoic-2' :5'- di (5 hydroxyethoxy) Q-m-bromobeflzoylamino anilide precipitated by the addition'oi! acid, filtered'oii. and dried.

4-m-bromobenzoyl'amino-2:fi-dicp-acetoxyethoxy) aniline (M. P. 103-104" C.) may be made by condensing m-bromobenzoylchloride with 2:5-

di(p -acetoxyethoxy) aniline in benzene in the 4. The compounds represented by the formula presence of potassium acetate. followed by nltra-.- H 002K401! tion in glacial acetic acid and reduction of the RNflr-iw:

resulting m-bromobenzoyl compound. -O c CzH40H well in cold water and boiled for 20 minutes in Example 8 in which R is the radical of a diazotizable aro- 3 parts of the new amide made accordingto matic amine whichis devoid of solubilizing Example '(are made into a paste with parts gmups- 01 50 Turkey red n which has been w 5. The compound represented by the formula traiised with sodium carbonate and 60 parts of co boiling water are added followed by 6 parts of sodium hydroxide solution (S. G. 1.31). The resuiting solution is diluted with 1000 parts of water containing 10 parts of sodium chloride and 50 parts of cotton yarn are immersed therea in for minutes, removed, squeezed well and N then introduced into' a bath containing 2 parts of diazotised 5-nitro-2-aminoanisole per 1000 0K 001E403 parts of solution. The cotton is turned for 20 2o minutes in the bath, removed. squeezed, rinsed (JO-EN a solution containing 2 parts of sodium car- 0,3403

bonate and 3 parts of neutral soap flakes per The compound represented y the formula 1000 parts of solution. A bluish-red shade of good light fastness is obtained. f 01 When; 4-chloro-2-aminoanisole, 4-chloro-2- N nitro-aniiine, or e-aminoanthraquinone is, used instead of 5-nitro-2eaminoani'sole, the following of! 00111011 shades are obtained:

co-nN nn-oc-cm-oO (hHeOH I 7. The compound represented by the formula 4-chloro-2-aminoanisole... Dull red 4-chloro-2-nitroaniline.... Brownish orange. Cl or-aminoanthraquinone Do.

Amine employed Shade obtained N As many apparently widely diflerent embodiit ments of this invention may be made without 1 departing from the spirit and scope thereof, it 4 on OCaHtO isto be understood that we do not limit ourselves to the specific embodiments thereof exco-rm 'NH-oc-cnroO We claim: cimon cent as defined in the appended claims:

1. The compounds represented by the formula 8. Cellulosic iiberdyed with the dye of claim 1.

OH OCzHtOH RNH: I I

CO-JINQNH-O c-(cnr-o)....'- D 0:11.011 in which X is one of a group consisting of hy- 9. Cellulosic fiber dyed with the dye of claim 2. drogen, alkoxy and halogen, n is an integer not 10. Cellulosic fiber dyed with the dye of greater than 2 and R is the radical of a diclaim3. azotizabie aromatic amine which .is devoid of 11. Cellulosic iiber dyed with .the dye of solubiiizing groups. claim 4. 1

2. A compound represented by the formula 12. Cellulosic flber dyed with the dye of Y claim 5. mm 011 1s. Cellulosic fiber dyed with the dye of H m claim6 I 14. Cellulosi fiber dyed with the dye of 2: claim '1.

can]! 15. The process which comprises applying to in which?! is One of Emuv mnsisting 9 cellulosic' fiber 'an anilide represented by the drogen, alkoiw and halogen, and R is the radical formula of a diazotizable aromatic amine which is devoid of solubilizing groups. 03 002114011 3. The compounds represented by the formula CO HN OH OCaHaOH c H OH RNH C0-HN NHOC- 003: '70

in which X is one of a group consisting of hy- CaHtOH drogen, alkoxy and halogen and n is an integer in which R- is the radlcal'of a diazotizable aronot greater than 2; and then coupling on the matie amine which is devoid of solubilizing fiber with the diazo of an aromatic amine which groups. 4 is devoid of solubilizing groups.

16. The process in accordance with claim 15 in which the diazo 0 the aromatic amine is applied in the form of a solution of the diazotizedamine.

17. The process in accordance with 'claim 15 in which the diazo of the aromatic amine is applied in the form of a solution of a stabilized compound of the diazotized amine.

18. Process comprising applying to cellulosic fibre a p'-acylated,2 :3-hydroxynaphthoic-2:5'- 10 di(p-hydroxyethoxy) anilide, in which the acyl group is the residue of an acid of the group consisting of benzoic acid, phenoxy-acetic acid and the nuclearly substituted alkoxy and halogen derivatives of said acids, and colouring the material by the application thereto of a diazo compound which is free of solubilising groups such as sulphonic acid or carboxylic acid groups.

GEOFFREY J. MARRIOTT. KENNETH HERBERT SAUNDERS.

v Certificate of Correction I Patent No. 2,262,464. r

GEOFFREY JONES MARRiOTT ET AL.

It is hereby certified that errors appear in the printed specification of the above I numbered patent requiring correction as follows: Page 3, second column, lines 66 to 70 inclusive, claim 15, strike out the formula and insert instead the followingpage 4, first column, line 10, claim 18, for -2:5- read -2:5-; and that the said Letters Patent should be read with these corrections therein that the savmemay conform to. the record of the case 1n the Patent Office.

Signed and sealed this 30th day of December, A. D. 1941.

[SEAL] HENRY VAN ABSDALE Acting Oommtss'zoner 0 Patents.

November 11, 1941. 

